Process for the synthesis of chlorinated, unsaturated hydrocarbons



Patented May 7, 1940 t v 1 UNITED STATES PATENT OFFICE.

PROCESS FOR THE SYNTHESIS OF CHLO- RBNI QATED, UNSATURATED HYDROCAB- Herman B. Kippcri Accord; Mass.

No Drawing. Application July 1, 1938, Serial No. 217,021

3 Claims. (Cl. 260-654) In my co-pending application, Serial No. 89,463, to redness was used to generate the oxides of niprocessing is described for the synthesis of chlotrogen. The step described, however, requires rinated, unsaturated hydrocarbons by simultanethe subsequent fractionation of the carbontetraous oxidation and chlorination of various grades chloride from the chlorinated oil and hence does 5 of petroleum hydrocarbons, condensed olefines, not offer the full advantages of smooth chlorina- 5 etc. tion which applicant had first expected through I have carried out similar syntheses of chlosuch treatment. rinated, unsaturated hydrocarbons by the action About seventy-five grams of the oxides of niof hydrochloric and nitric acids on petroleum hytrogen were passed through a thousand grams of drocarbons and with the aid of powerful stirthe fuel oil and heated to about fifty degrees C. 10

ring during the carrying out of reaction. and simultaneously about one hundred grams of For instance, one thousand grams of a heavy chlorine were passed into the same. The above so-called No. 2 house fuel oil was heated to about method was employed by applicant for direct seventy degrees C. and one hundred and fifty chlorination and oxidation without the use of grams of a 1.20 specific gravity hydrochloric acid carbontetrachloride. 15 was added to the vesselcontaining the oil. About When using hydrochloric acid for the chloseventy-five grams of a 1.5 specific gravity fumrination work, the nitric acid was found to have -ing nitric acid was then added to the reaction been about sixty to sixty-five percent decomposed vessel or beaker slowly, or during a period of about or utilized in the oxidation step. When using an hour. Thorough stirring of the contents was chlorine, about a ninety percent utilization was 20 maintained during the carrying out of reaction. found. If the oil is heated to about one hundred Considerable heat is developed and some fairly degrees utilization of t e n c acid Will be hard tar or resin-like products are produced in c d but the ProductiOn f arry 01 Semit 11 being t t resinous matter is increased.

si i k was repeated with k r n gas- The oils which I have fabricated were subse- 25 oline, lighter fuel oils and oil condensed from olequently washed with water and dilute alkali or finic hydrocarbons. A number of experiments ammonia. were also carried out in treating chlorinated oils I also used a thirty percent hydrogen peroxide made by direct chlorination through subjecting solution in place of the nitric acid for the oxidathem to the oxidizing treatments produced by tion agent. A thousand grams of the oil was sim- 30 nitric acid but without the use of hydrochloric ilarly heated to fifty or a hundred degrees 0., acid. For instance, a heavy fuel oil chlorinated about one hundred and fifty grams of hydrowith. about twenty pe c of ne was Sub chloric acid were added and two hundred grams J' to oxidation y e P c Of fuming of the hydrogen peroxide were slowly added untllC acid at about seventy degrees during an hour der vigorous tirring of the reaction emulsion, 35

p i d und r t u tir n If th reaction The reaction was also carried out similarly exveSSel w o the treatment period might of cept that chlorine, in place of hydrochloric acid, Course be Shortenedwas slowly run into the oil as the peroxide solu- Chlorination and oxidation were also produced tion was added.

40 by passing chlorine the fuel and adding Ozone would probably act similarly toward 40 nitric acid simultaneously. About fifteen percent duction of chlorinated unsaturated hydrocar of chlorine was passed through thevheavy fuel on bons, as well as any other source of chemically acof the grade noted and about eight percent of five ox I ygen utilized with ChlOllIle or hydrochloric fummg mum and was slmultaneously added acid. Nitrosyl and nitroxyl chlorides may also h gg l gf fi gffi gl i ai f g ig z i s be used fully satisfactorily for production of the 45 degrees C. and thorough stirring was employed. Oils in question: I have t out small experi' Applicant has also used the oxides of nitrogen ments to estabhsl} Such pomt" in place of nitric acid for this work. He further I am now testmg out the 011s fabncated in absorbed the said oxides in carbontetrachloride palms d m film coatmgs am 115mg f Such 50 and the chlorine was also dissolved in the same Work the dryers and p y nts described in solvent. The treatment of the fuel oil was then my applications, Serial ers 6 00,8 8: carried out by adding the carbontetrachloride so- 4; 9 lutions under powerful stirring for simultaneous 352; and 212,389. I

5 oxidation and chlorination. Lead nitrate heated Naturally, other hydrocarbon oils, as gas oils,

other temperatures and pressures, and other percentages of reaction compounds, might be employed. Such combinations might be expanded ad infinitum without departing from the inherent nature of my invention.

I claim:

1. In a process for the chlorination and dehydrogenation of petroleum hydrocarbons to produce unsaturated chlorinated hydrocarbons, the step of treating the said hydrocarbons simultaneously with chlorine and nitric acid at temperatures under one hundred and fifty degrees centigrade.

2. In a process for the chlorination and dehydrogenation of liquid petroleum hydrocarbons to 

